JP2016530229A - How to control waterborne pests - Google Patents

Abstract

The present invention discloses a method for controlling surface aquatic pests, particularly cyanobacteria and harmful algal bloom (HAB) in aquatic systems, the method comprising a water disinfectant, preferably an oxidizing compound, and a flotation agent comprising a flotation agent. Diffusing the composition over the water surface of an aquatic system. The invention further relates to compositions and methods for their preparation and uses. [Selection figure] None

Description

The present invention is in the field of water sterilization.
Prior art

References that are considered relevant as background art for the presently disclosed subject matter are listed below:
Berg, K .; A. , Lyra, C, Sivonen, K .; Paulin, L .; Suomalainen, S .; Tuomi, P .; , And Rapala, J. et al. (2008) High diversity of intensive heterobacteria in association with cyanobacterial waters. IMEJ3: 314-325.
Broza, M.M. And Halpern, M .; (2001) Chironomid egg / m2asses and Vibrio cholerae. Nature 412: 40.
Deng L. And Hayes P.M. K. (2008) Evidence for cyanophages active again-blooming fresh water cyanobata. Fresh Water Biology 53: 1240-1252.
Di Domenico, D.D. , Ruggeri, L .; , And Trentini, M .; (2006) The use of sodium hypochlorite as obeague against Aeds albopictus. Journal of the American Mosquito Control Association 22: 346-348.
Drabkova, M .; Marsalek, B .; , And Admiral, W .; (2007) Photodynamic thermal against cyanobacteria. Environ Toxicol 22: 112-115.
Eiler, A.M. And Bertilson, S .; (2004) Composition of freshwater community communities associated with cyanobacterial blocks in four Swedish lakes. Environmental Microbiology 6: 1228-1243.
Falconer J. et al. R. Beresford, A .; M.M. , And Runnegar, M .; T.A. (1983) Evidence of liberty by toxin from a blue of the blue-green alga, Microcystis aeruginosa. The Medical Journal of Australia 1: 511.
Gardes, A.M. , Iversen, M .; H. Grossart, H .; P. Passow, U.S.A. , And Ulrich, M .; S. (2010) Diatom-associated bacterium required for aggregation of Thalassiosira weisslogiii. ISMEJ Hatchett, S.J. P. (1946) Chlorine as a possessive for Aedes aegypti eggs. Public Health Reports (1896-1970) 61: 683-685.
Hulebusch, E .; V. , Deluchat, V .; Chazal, P .; M.M. , And Baudu, M .; (2002) Environmental impact of two successful chemical treatments in a small shallow eutrophic lake: Part II. Case of copper sulfate. Environmental Pollution 120: 627-634.
Iredale, R.A. S. McDonald, A .; T.A. , And Adams, D .; G. (2012) A series of experiments aimed at clarifying the mode of action of barley straw in cyanobacterial growth control. Water Research 46: 6095-6103.
Jacups, S.M. P. Ball, T .; S. Paton, C .; J. et al. Johnson, P .; H. , And Ritchie, S .; A. (2013) Operational use of household to "crush and release" Journal of Medical Entology 50: 344-351.
Jones, B.M. E. Grant, W .; D. , Duckworth, A .; W. , And Owenson, G .; G. (1998) Microdiversity of soda lakes. Extremophiles 2: 191-200.
Kaplan, A.M. Harel, M .; Kaplan-Levy, R .; N. Hadas, O .; , Sukenik, A .; , And Dittmann, E .; (2012) The language spokes in the water body (or the biological role of cyanobacterial toxins). Frontiers in Microbiology 3.
Kolmakov, V.M. I. (2006) Methods for prevention of mass development of the cyanobacterium Microcystis aeruginosa Kutz emend. Elink. in aquatic systems. Microbiology 75: 115-118.
Matthijs H.M. C. P. , Visser P. M.M. Reeze B. Meeuse J .; Slot P. C. Wijn G., et al. , Talens R. Huisman J .; (2012) Selective suppression of harmful cyanobacteria in an entire lake with hydrogen peroxide. Water Research 46: 1460-1472.
Sigee, D.M. (2005) Biodiversity and Dynamic Interactions of Microorganisms in the Aquatic Environment. In Freshwater Microbiology. Chichester, UK: John Wiley & Sons, pp. 328-338.
Swaen, G / M2. , Van Vliet, C, Langen JJ. , And Sturmans, F.A. (1992) Cancer morality licensed herbicide applicators. Scandinavian journal of work, environment & health 18: 201-204.
Xiao, X. Huang, H .; , Ge, Z. , Runge, T .; B. Shi, J .; , Xu, X. (2014) A pair of chiral flavonignans as novel anti-cyanobacterial allicultially dehydrated barleythrough (Hordeum vulgarare) Environmental Microbiology 16: 11238-1251.

  Approval of the above references herein should not be inferred to imply that they are more or less related to the patentability of the presently disclosed subject matter.

Photosynthetic microorganisms tend to form seasonal blooms in water bodies such as ponds, lakes, sewage reservoirs and the ocean. These blooms are defined by a significant increase in the number of cells that can reach up to 10 ⁶ to 10 ⁷ cells / mL and chlorophyll a over 50 μg / L. This phenomenon can become apparent to the naked eye when the water turns dark green, red or brown. Seasonal blooms mainly consist of microorganisms that can convert light energy by photosynthesis, but also coexist with many other microorganisms that maintain the entire community (Gardes et al., 2010). In some cases, depending on biological and abiotic conditions, some species, cyanobacteria, also known as cyanobacteria, use their gas vesicles to position themselves on the water surface, Form a film (also called scum or mat). Cyanobacteria are a wide variety of oxygen-producing photosynthetic prokaryotes with diverse physiological tolerances and broad ecological tolerance, which contributes to their ability to compete across a wide range of environments. Yes. Over 40 years, the abundance of these microorganisms has increased worldwide in lakes, reservoirs, rivers and brackish environments. Cyanobacterial blooms produce a musty odor and more seriously produce toxins. The cyanobacterial harmful algal bloom (CHAB) represents a eutrophication problem as well as the secretion of enormous metabolites, some of which are most toxic to eukaryotes (Kaplan et al., 2012). And for health institutions it means a warning situation.

Currently, several means for treating algal blooms, such as continuous treatment with aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) and copper sulfate (Hullbusch et al., 2002), peroxides (Drabkova et al., 2007), or Herbicides (ie diuron, simazine, atrazine) are used. However, these treatments are associated with serious environmental impacts (Falconer et al., 1983; Kolmakov, 2006; Swaen et al., 1992) and costly (Al ₂ (SO ₄ ) ₃ treatment is 1 square km. Estimated per US $ 750,000 to US $ 1,000,000).

  Thus, available treatments are mainly used in artificial ponds, pools and small shallow lakes where the ecological aspects of overdose are not critical. These treatments are not suitable for large waters and are not suitable for repeated use because of toxic and ecological effects, relatively high costs, and high input requirements for uniform dispersion.

  Another means to prevent CHAB is to throw barley or rice straw into the aquatic ecosystem, but this effect has not been steady (Iredale et al., 2012). The recently discovered active compounds (flavonolignansarcolin A and B) (Xiao et al., 2014) have shown their dissolution potency against Microcystis aeruginosa. However, these active compounds are not commercially available and the necessary environmental and regulatory approvals have not yet been obtained.

  Algae virus, a lytic virus that specifically attacks cyanobacteria, has been hypothesized, but has never been identified or used in the past (Deng and Hayess, 2008).

Matthijs et al. (2012) used a dispersion apparatus to treat the entire volume of a shallow lake of 0.12 square kilometers with about 60 μM liquid H ₂ O ₂ . This approach is expensive due to the high cost equipment, requires a lot of time and is dangerous due to the use of liquid hydrogen peroxide. The chemical was also recorded in the lake water two days after treatment. Furthermore, frequent exposure to H ₂ O ₂ over a large area and frequently can induce cyanobacterial resistance to this compound in the long term.

Chironomidae (Diptera; Chironomidae; Chironomidae) is the most abundant insect species in freshwater around the world. Chironomids undergo complete transformation in four life stages; three are aquatic (eggs, larvae, pupae) and the last is the terrestrial adult stage. Females lay egg masses (consisting of 400-1,000 eggs) embedded in a thick jelly-like substrate at the edge of the body of water.

Chironomid (aka non-nutka) causes serious ecological and economic harm. A large group of adult chironomids arising from aquatic habitats in or near urban areas affects tourism and real estate values and is associated with human allergic reactions. As larvae, chironomids can clog water pipes and reach home users' water supply systems (“red worms”). In addition, chironomid jelly-like egg masses have been reported to play a role as natural pathogens of Vibrio cholerae (Broza and Halpern (2001)). At present, efforts to prevent cholera depend on a combination of public health measures. Pesticides used for chironomid larvae have been found to be adaptable and resistant to chironomids when used continuously, so their success is limited. In addition, pesticides have a wide range of specificities and can harm the environment, including humans.

  The present invention is based on the surprising discovery that floating formulations of various bleaching agents are effective in reducing cyanobacterial populations in treated water. In addition, this floating formulation has shown efficacy as a marine insect ovicide and has drastically reduced the number of healthy larvae that hatch from eggs.

Accordingly, the present invention, in its first aspect, provides a method for controlling surface aquatic pests in an aquatic system, the method comprising:
a. Obtaining a composition comprising at least one water disinfectant that is an active agent releasing compound and at least one flotation agent;
b. Treating the aquatic system with this composition under conditions that result in a reduction, inhibition or elimination of the growth of the pests described above in the aquatic system.

  In one embodiment, the at least one water disinfectant is an oxidizing water disinfectant.

  In one embodiment, the at least one water disinfectant is selected from the group consisting of a chlorine releasing agent, a bromine releasing agent, a peroxide-based compound, a copper salt, an aluminum salt, and any combination thereof.

In a specific embodiment, the water disinfectant is calcium hypochlorite (Ca (OCl) ₂ ) or sodium dichloroisocyanurate (NaDCC).

  In one embodiment, the flotation agent is selected from the group consisting of cellulose derivatives, plant biomass, saturated hydrocarbons, resinous materials, foams, and natural or synthetic latex.

  In a specific embodiment, the flotation agent is wood flour.

  In another specific embodiment, the flotation agent is paraffin.

  In another specific embodiment, the flotation agent is rosin.

  In another specific embodiment, the flotation agent is an extruded polystyrene foam or expanded polystyrene foam.

  In another specific embodiment, the flotation agent is a silicone foam.

  In certain embodiments, the amount of the at least one water disinfectant is about 10% (w / w)%, or about 20%, or about 30%, or about 40%, or about 50% by weight or more.

  In certain embodiments, the composition is in the form of particles, granules, flakes, powders, pellets, pills, solutions or combinations thereof.

  In one embodiment, the pest growth is selected from the group consisting of cyanobacterial growth, algae growth, microbial growth, plankton growth, and aquatic insects.

  In one embodiment, the processing step follows detection of harmful algal blooms in the aquatic system.

  In a specific embodiment, the processing is performed early in the bloom development.

  In another embodiment, the processing step is performed when growth of the pest is detected.

In a specific embodiment, the pests are cyanobacteria, said water disinfectant, the concentration of between about 0.005 g / ^{m 2} and about 50 g / ^{m 2} or about the active agent, 0.5 ppm And at a concentration between about 50 ppm.

  In one embodiment, the treatment described above results in trace amounts of active compound measured in water after 0.5 hour, 1 hour, 2 hours, 3 hours, 24 hours or after each treatment. .

  In a specific embodiment, the trace amount of active compound does not exceed 3 ppm when measured more than 24 hours after each treatment.

  In another embodiment, the pest is a water-borne insect and the disinfectant is administered at a concentration between about 50 ppm and about 1000 ppm.

  In a specific embodiment, the water-inhabiting insect is a genus Culex sp., Aedes sp., Anopheles sp. Or Chironomidae sp.

  In certain embodiments, the disinfectant described above acts as an ovicide.

  In one embodiment, the processing step includes a single dose, two doses, or multiple doses of a water disinfectant.

  In certain embodiments, the processing steps are three times a day, or twice a day, or once a day, or once a week, or once every two weeks, or once every three weeks, or once a month. One or more intervals are performed.

  In a specific embodiment, the processing step is performed once a day or twice a day for a period of 1 day, 2 days, 3 days, 4 days, 5 days or more.

  In one embodiment, two or more doses are made with the same or different disinfectants.

  In certain embodiments, this treatment is performed by a manual or mechanical spreader or by diffusing the liquid from, for example, a boat or airplane.

  In another aspect, the invention provides a composition for use in controlling aquatic pests in an aquatic system, the composition comprising at least one water disinfectant that is an active agent releasing compound and at least one water disinfectant. Contains floating agent.

  In one embodiment, the at least one water disinfectant is an oxidizing water disinfectant.

  In one embodiment, the at least one water disinfectant is selected from the group consisting of a chlorine releasing agent, a bromine releasing agent, a peroxide-based compound, a copper salt, an aluminum salt, and any combination thereof.

  In a specific embodiment, the water disinfectant is calcium hypochlorite or NaDCC.

  In one embodiment, the flotation agent is selected from the group consisting of cellulose derivatives, plant biomass, saturated hydrocarbons, resinous materials, foams, and natural or synthetic latex.

  In a specific embodiment, the flotation agent is wood flour.

  In another specific embodiment, the flotation agent is paraffin.

  In another specific embodiment, the flotation agent is rosin.

  In another specific embodiment, the flotation agent is an extruded polystyrene foam or expanded polystyrene foam.

  In another specific embodiment, the flotation agent is a silicone foam.

  In certain embodiments, the amount of the at least one water disinfectant is about 10%, or about 20%, or about 30%, or about 40%, or about 50% or more by weight of the total composition. It is.

  In certain embodiments, the composition is in the form of particles, granules, flakes, powders, pellets, pills or solutions.

  In one embodiment, the pest growth is selected from the group consisting of cyanobacterial growth, algae growth, microbial growth, plankton growth, and aquatic insects.

  In one embodiment, the composition is administered following detection of harmful algal blooms in an aquatic system.

  In a specific embodiment, the composition is administered early in the bloom episode.

  In another embodiment, the processing is performed when growth of the pest is detected.

In a specific embodiment, the pests are cyanobacteria, at least one water disinfectant described above, a concentration of between about 0.005 g / m ² and about 50 g / m ² or active agents, Administered at a concentration between about 0.5 ppm and about 50 ppm.

  In one embodiment, administration of the above composition to the aquatic system comprises trace activity measured in water at 0.5 hours, 1 hour, 2 hours, 3 hours or after each treatment. Resulting in a compound.

  In a specific embodiment, the trace amount of active compound does not exceed 3 ppm when measured more than 24 hours after each treatment.

  In another embodiment, the pest is a surface inhabiting insect and the at least one water disinfectant is administered at a concentration between about 50 ppm and about 1000 ppm.

  In a specific embodiment, the surface-inhabiting insect is a genus Culex sp., Anopheles sp. Or Chironomidae sp.

  In certain embodiments, the disinfectant described above acts as an ovicide.

  In one embodiment, the composition is administered once, twice or more to the aquatic system.

  In certain embodiments, the composition is three times a day, or twice a day, or once a day, or once a week, or once every two weeks, or once every three weeks, or once a month. It is administered once or at longer intervals.

  In a specific embodiment, the composition is administered once daily or twice daily for a period of 1 day, 2 days, 3 days, 4 days, 5 days or more.

  For a better understanding of the subject matter disclosed herein and to illustrate how it may actually be performed, the embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings. Describe in.

It is an image of a glass bottle filled with CHAB. (A) Before treatment, (B) After overnight treatment with a suspension of calcium hypochlorite. 3 is an image of glass bottles filled with CHAB and treated with various concentrations of calcium hypochlorite. (A) No treatment, (B) Treatment with 0.5 g / square m Ca (OCl) ₂ , (C) Treatment with 1.0 g / square m Ca (OCl) ₂ , (D) 5.0 g / square Treat with m Ca (OCl) ₂ . It is a graph showing the density | concentration (microgram / L) of the chlorophyll a in the water surface as a function of time (days). It is a graph showing the density | concentration (microgram / L) of the chlorophyll a in the water depth of 50 cm as a function of time (days). It is a graph showing pH measured value as a function of time (days). As the time (in days) function is a graph showing the concentration of dissolved oxygen in water (MgO 2 / _L). It is the image of a typical enclosure. (A) No processing (B) Processing with 3 capsules (C) Processing with 6 capsules and (D) Processing with 9 capsules. Figure 2 is a graph showing cyanobacterial concentrations (cells / mL) in enclosures treated with 3, 6 or 9 capsules or untreated (0) at two time points (12:00 and 15:00). It is an image of the water surface of the enclosure. (A) No processing, (B) Processing with 6 capsules. Figure 3 shows an image of a vial containing water taken from the surface of the enclosure after being treated with two capsule doses. Left vial-no treatment, subsequent vials treated with 3, 6 and 9 capsules from left to right, respectively.

  The present invention relates to a floating composition containing a bleaching compound (or oxidizing agent) suitable for controlling water-borne pests.

  In particular, the present invention, first and foremost, is suitable for the control of pests living on the surface of water containing cyanobacterial harmful algal bloom (CHAB), calcium hypochlorite, sodium dichloroisocyanurate (NaDCC) or sodium percarbonate (or The present invention relates to a floating diffusible preparation containing other algicidal agents that act upon contact, and a method for preparing the preparation.

  The present invention relates to a suspension of cyanobacteria in which a suspension of calcium hypochlorite or NaDCC has a “total Cl concentration” (total Cl concentration in the water column) that is much lower than the acceptable concentration of chlorine in drinking water. This is based in part on the surprising discovery that it has shown excellent efficacy against mats.

  Hypochlorite and other oxidants have been used for decades as purifiers in drinking water supply systems. Similarly, in small bodies of water such as swimming pools and recreational pools, algae and bacteria are often purified by systematic treatment with high concentrations of hypochlorite. This solution is due to the high costs associated with the large amount of compounds required and the nonspecific lethal effects of bleach on the fauna and flora of the entire ecosystem, resulting in large catchments such as lakes or open water bayou. Apparently not suitable for the region.

  The present invention is based on the recognition that the deleterious effects of using a water disinfectant that acts upon contact can be improved by reducing the actual concentration of the compound in the water column. This is accomplished by maintaining a gradient of disinfectant (eg, hypochlorite or hydrogen peroxide) in the water column by sustained release of the compound from the diffusive suspension formulation. Disinfectant concentration gradients are generated by the diffusion of compounds in water and optionally also by rapid interaction with organic substances (including phytoplankton) in water. Cyanobacterial masses are located as mats on the surface of the water, so the use of the floating composition of the present invention on the surface of the water can prevent the development of potential algae toxic blooms.

  This novel treatment concept stems from the surprising discovery that relatively small amounts of oxidized compounds are sufficient to cause overwhelming reactions by phytoplankton and especially cyanobacterial populations. This effect can be achieved by using a suspension formulation of the oxidized compound. When repeated at a certain frequency (due to the initial cyanobacterial content and composition, and the total load of organic matter in the water), the number of cyanobacterial cells begins to decrease, eventually leading to the collapse of the HAB population, and any Cause water column colonization by competing with non-pests. This method allows simple processing with very low oxidant dispersion input requirements and facilitates efficient use of large quantities of dispersion methods (eg, boats and pesticide spray planes). In addition, due to the low dose of oxidant and due to the large organic loading in the treated water, the total concentration of effective oxidant in the water is the concentration in the treated drinking water (1-3 ppm allowed by the regulatory body). Resulting in a safe and simple process that is significantly lower than the available chlorine) and has little adverse environmental impact.

  While not wishing to be bound by theory, hypochlorite reacts with abundant organic material on the water surface in the water column and therefore does not accumulate in the water column. Every molecule of chlorine reacts with organic substances present in aquatic systems, so that effective or total chlorine concentrations are almost undetectable.

The method of the present invention provides a simple and inexpensive solution compared to current processes using aluminum sulfate. The solution provided by the present invention is about 15-20 times cheaper than current Al ₂ (SO ₄ ) ₃ treatment, is much more effective, and is much less toxic to the environment.

  As a result of the treatment, the number of algae and cyanobacteria can be significantly reduced. As a result, toxin release, commonly associated with cyanobacterial cell lysis at the end of the season, is avoided or significantly reduced, while avoiding the harmful effects of CHAB on water quality, while To avoid widespread harm to aquatic life.

Accordingly, the present invention provides a method for controlling water-borne pests in an aquatic system, the method comprising:
(A) obtaining a composition comprising at least one water disinfectant that is an active agent releasing compound and at least one flotation agent;
(B) treating the aquatic system with this composition under conditions that result in the reduction, inhibition or removal of the above pests in the aquatic system.

  As used herein, the term “inhibiting aquatic pests” relates to reducing, inhibiting, preventing or eliminating the growth of such pests in an aquatic system.

  As used herein, the term “pest” refers to algae (eg, cyanobacteria harmful algal bloom (CHAB)), organisms that cause phenomena such as red tides (due to dinoflagellates) or sea bubbles, bacteria , Plankton, phytoplankton, surface-inhabiting insects (ie, butterfly, Chironomidae (Chironomidae) or mosquitoes such as adults, eggs or larvae of the mosquito or stefense anopheles) Thus, non-limiting examples of water-inhabiting insects include Culex sp., Aedes sp., Anopheles sp., And Chironomidae sp. ).

  In a specific embodiment, the pests are cyanobacteria and cyanobacterial harmful algal bloom (CHAB).

  As used herein, the term “algal bloom” relates to the rapid increase or accumulation of algal populations (generally microscopic) in aquatic systems. Algal blooms can occur in freshwater as well as marine environments and are also referred to as scum or floating algae mats. The term “hazardous algal bloom” (HAB) refers to an algal (or cyanobacterial) bloom that causes toxin production, physical damage to other organisms, or adverse effects on other organisms by other means. About. This term refers to green algae, and (but is not limited to) microcystis, anabena, planktosria, nenjumo, nodularia, uremo, cylindroperm, plankthrix, aphanizomenon, ringbia and other cyanobacteria, and anabena Include all large or small photosynthetic organisms, including species such as floss aqua and planktonica, and harmful marine dinoflagellates associated with red tides within the harmful marine algal bloom.

  Compositions of the present invention, and in specific embodiments, compositions comprising hypochlorite or hydrogen peroxide affect not only algal blooms, but also commensal bacterial species associated with CHAB. It is known that different bacterial species play a major role in the presence of CHAB (Eiler and Bertilson, 2004; Jones et al., 1998; Sigee, 2005). Some of them, independently of each other, have adverse health effects on humans and animals (Berg et al., 2008).

  Furthermore, the compositions of the present invention, particularly those comprising hypochlorite or hydrogen peroxide, have an indirect adverse effect on insects. In particular, insects that inhabit the surface of the water interact in at least part of their life cycle. Examples include chironomids and anopheles, but are not limited thereto.

  In certain embodiments, the methods of the invention target non-motile eggs of insects. Hypochlorite at a concentration of 250-500 ppm did not hatch 95% of the egg population. Other eggs hatched early and most of the hatched larvae did not grow into larvae.

  While not wishing to be bound by theory, not only does it affect the chironomid population by removing egg clumps from the environment, but it also spreads or is ingested in the water and thus propagates to humans ( The ability of V. cholerae) can also be reduced.

  As used herein, the term “aquatic” refers to lakes, rivers, springs, ponds (eg, fish ponds), waterways, aquariums, hydroponic systems, water retention systems or water transport systems, reservoirs, natural drinking water systems. Include natural or artificial systems such as brackish water environment, sewage and ocean.

  As used herein, the term “water disinfectant” relates to a compound that can remove, inactivate or kill microorganisms in the water.

  In a preferred embodiment, the water disinfectant is an active drug releasing compound. In another embodiment, the water disinfectant is an oxidizing water disinfectant.

Non-limiting examples of water disinfectants according to the present invention include chlorinated compounds (also referred to as “chlorine releasing agents”) (eg, hypochlorite (OCT), calcium hypochlorite, sodium hypochlorite , Sodium dichloroisocyanurate (NaDCC, dihydrate, monohydrate or anhydrous), dichlorodiphenyltrichloroethane (DDT)), copper sulfate, bromine-based compounds (also called “bromine-releasing agents”), iodine (I), iodine Fall, potassium permanganate (KMnO ₄ ), and peroxide generating compounds (eg, hydrogen peroxide, sodium percarbonate, calcium peroxide, crystalline hydrogen peroxide-PVP complex, sodium perborate (tetrahydrate) Or monohydrate) and peracetic acid). Preferably, the water disinfectant is an oxidizing agent that reacts with water and with organic substances in the water, thereby producing non-toxic products that do not accumulate or change the aquatic environment.

  For example, suitable reactive chlorine-containing or bromine-containing oxidizing agents include heterocyclic N-bromoimides and N-chloroimides such as trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and dichloroisocyanuric acid, and potassium and sodium And salts thereof having a water-solubilizing cation such as sodium dichloroisocyanurate (NaDCC) dihydrate or anhydrous NaDCC. Further water disinfectants include chloramine T (N-chloro-4-methylbenzenesulfonamide sodium salt), dichloramine T (N, N-dichloro-4-methylbenzenesulfonamide), or chlorine releasing quaternary ammonium compounds. (For example, benzalkonium chloride, benzethonium chloride and cetylpyridinium chloride). Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable. Dry, granular, such as lithium hypochlorite, sodium hypochlorite or calcium hypochlorite and lithium hypobromite, sodium or calcium hypobromite, and trisodium chlorinated phosphate Water-soluble anhydrous inorganic salts are also suitable for use herein.

  For example, suitable peroxide compounds include organic peroxy acids. The peroxyacid that can be used in the present invention is a solid, preferably a substantially water-insoluble compound. In one embodiment, common monoperacids useful herein include peroxybenzoic acid and ring-substituted peroxybenzoic acid (eg, peroxy-α-naphthoic acid) or aliphatic monoperoxyacid and substituted aliphatic monoperoxy. Alkylperoxyacids and arylperoxyacids such as acids (eg peroxylauric acid and peroxystearic acid) are mentioned.

  Inorganic peroxygen generating compounds may also be suitable as nuclei for the particles of the present invention. Examples of these materials are peroxomonosulfate, copper sulfate, perborate monohydrate, perborate tetrahydrate, and percarbonate salts.

  In another embodiment, the water disinfectant is an aldehyde (eg, formaldehyde or glutaraldehyde) and its solidified compound.

  In one embodiment, the compositions of the present invention include, but are not limited to, any mixture of the aforementioned compounds, such as copper sulfate and any hypochlorite compound. Preferably, such a mixture will provide a synergistic effect.

  In one embodiment, the method of the present invention comprises sequential administration of the composition of the present invention, with a different water disinfectant used for each administration.

  The term “water disinfectant” also includes bleach or bleach compounds.

Non-limiting examples of active agents released by the active agent releasing compound include chlorine (Cl ₂ ), chlorine dioxide (ClO ₂ ), ozone (O ₃ ), halogen (eg bromine (Br ₂ ), bromine chloride (BrCl), Metals (eg copper (Cu ²⁺ ), silver (Ag ⁺ ), alum, phenol, alcohol, soap and detergent.

  In a specific embodiment, the water disinfectant is any compound suitable for water sterilization that produces hypochlorous acid or hydrogen peroxide as the active compound.

  In a specific embodiment, the water disinfectant is calcium hypochlorite, sodium dichloroisocyanurate (NaDCC) dihydrate, or percarbonate.

  As used herein, the term “floating agent” relates to a compound capable of floating on the water surface. Non-limiting examples of flotation agents include cellulose derivatives, plant biomass, saturated hydrocarbons, resinous materials, foams, gelling agents, and natural or synthetic latex.

  In one embodiment, the flotation agent is wood flour (also called sawdust). In a specific embodiment, the composition comprises sawdust and calcium hypochlorite granules. The composition is prepared, for example, by adding calcium hypochlorite granules (eg 14-50 mesh) to the sawdust, partially occluding the compound with a silicone adhesive, thoroughly mixing, and then crushed to the desired granules. Make the diameter.

  In one embodiment, the flotation agent is paraffin. In a specific embodiment, the composition comprises calcium hypochlorite and paraffin. The composition is prepared, for example, by mixing calcium hypochlorite powder with paraffin in a 1: 2 weight ratio at the paraffin melting point and then extruded or cooled to 3-4 mm flakes.

  In one embodiment, the flotation agent is rosin. In a specific embodiment, the composition comprises calcium hypochlorite and rosin. The composition is prepared, for example, by mixing calcium hypochlorite powder with rosin in a 1: 2 weight ratio at the rosin melting point and then extruded or cooled to 3-4 mm flakes.

  The flotation agent may be a foam, for example any suitable oxidation-resistant foam-forming agent, for example a styrofoam or silicone foam.

  Thus, in one embodiment, the flotation agent is an extruded polystyrene foam or expanded polystyrene foam. In a specific embodiment, the composition comprises calcium hypochlorite and extruded polystyrene foam or expanded polystyrene foam. The composition is prepared, for example, by mixing calcium hypochlorite granules with an adhesive polymer preform solution and then curing.

  In another embodiment, the floater is a silicone foam. In a specific embodiment, the composition comprises calcium hypochlorite and silicone foam. The composition is prepared, for example, by mixing calcium hypochlorite granules with an adhesive polymer preform solution and then curing.

  In a specific embodiment, the suspending agent is an aqueous foam solution containing foam generating chemicals that can form a foam when mixed with a gas, such as air.

  In a specific embodiment, the composition of the present invention comprises an aqueous foam containing chlorine peroxide. An aqueous solution containing a disinfectant and capable of forming a foam is prepared, for example, by adding a blowing agent, ie a suitable surfactant, to the water. Chlorine peroxide may then be added to this solution, or peroxidized in situ by reacting an oxidizing agent, or an acid form of a cation exchange resin, or an acid with a metal chlorite dissolved therein. Chlorine may be generated.

  The resulting foam solution can then be foamed by mixing with air in the foam generator.

  In another embodiment, the flotation agent is a gelling agent such as hydroxypropyl methylcellulose. In a specific embodiment, the composition comprises dichloroisocyanuric acid sodium salt dihydrate (NaDCC) and hydroxypropyl methylcellulose.

  In certain embodiments, the composition may further comprise at least one binder, such as glyceryl stearate. While not wishing to be bound by theory, the addition of glyceryl stearate reduces pellet brittleness and increases buoyancy.

  In certain embodiments, the composition may further comprise at least one swelling agent, such as sodium chlorite, citric acid or sodium bicarbonate.

  Without wishing to be bound by theory, sodium bicarbonate and citric acid react upon exposure to water to release carbon dioxide, thereby further reducing the dissolution time of the compound.

  Thus, in one specific embodiment, the composition comprises NaDCC, hydroxypropyl methylcellulose, glyceryl stearate, and sodium chlorite or citric acid and sodium bicarbonate.

  In another embodiment, the composition comprises calcium hypochlorite coated with at least one thin film forming latex in hydrocarbon. The density of the coated particles depends on the porosity of the calcium hypochlorite pellets and the properties of the coating.

  The amount of the at least one water disinfectant may be about 10%, or about 20%, or about 30%, or about 40%, or about 50% or more by weight of the total composition.

  In certain embodiments, the composition can be prepared by mixing, compressing, curing, or coating to form solid particles.

  In certain embodiments, the composition is in the form of particles, granules, flakes, powders, pellets, pills, or solutions.

  In one embodiment, the above processing step (b) is performed by dispersing the composition on the water surface. Dispersion can be done by spraying the composition onto an aquatic system, for example by making an aerosol.

  In one embodiment, the process begins early in the bloom season, optionally under a periodic monitoring system.

  In a specific embodiment, the composition diffuses before or during bloom onset to prevent the development of potentially toxic blooms. The frequency of treatment may be daily, weekly or monthly, depending on, for example, organic loading, various other phytoplankton and microbial populations and types of harmful microorganisms.

  The treatment is repeated for several days, stopped and may then be resumed if the cell count rises.

  The algae mat is swept away on the surface of the water by water flow and wind. The buoyant formulation of the present invention moves with its target, so only the area where algae accumulate is treated and not the whole water surface.

  Effective treatment protocols can be determined by one skilled in the art according to local conditions in the aquatic system. The treatment may be provided as a single variance or as a polydisperse. The frequency of treatment is determined by local conditions, for example, three times a day, or twice a day, or once a day, or once a week, or once every two weeks, or once every three weeks, or It may be once a month, or longer or shorter intervals. In one embodiment, the treatment is performed once in the early season of cyanobacteria appearance and repeated as necessary.

  Reduction, inhibition or removal of algae growth can be easily determined using various methods. Non-limiting examples include visual detection, eg, by examining the color and / or viscosity of water; analysis of genetic markers, eg the presence of specific DNA from these organisms, such as DNA encoding ribosomes Analysis of quantity; measurement of chlorophyll a content; microscopic measurement of cyanobacterial cell number; measurement of dissolved oxygen concentration in water; or measurement of pH in water, where an increase in pH represents an increase in the number of cyanobacterial cells.

In one embodiment, the total concentration of oxidant (eg, calcium hypochlorite or NaDCC) in aquatic water is well below the acceptable chlorine level in the drinking water, preferably between 0.003 mM and 0. 0.03 mM, or 0.05-50 g / m < ² > of the water surface or below the water surface, or between about (0.5 ppm) and about (50 ppm) of the active agent.

For example (see Examples 1 and 2 below), we, the water level polluted water obtained from a small pond contaminated Jerusalem zoo in blue-green algae in excess of 10 ⁹ cells / mL, only 5g It has been shown that the use of / m ² is sufficient for total removal of the algal mat. For comparison, taking the shallow Green Lake (Seattle, USA) with a surface area of 1.05 · 10 ⁶ m ² and a water volume of 4.12 · 10 ⁶ m ³ , the acceptable range of hypochlorite in drinking water Only 5 tons of Ca (OCl) ₂ suspension formulation is used compared to 44 tons of comparable non-floating formulation at

  Furthermore, for enclosures with a capacity of about 270 liters, the use of only 1.2 g or 1.6 g NaDCC was sufficient for total removal of cyanobacterial contamination (shown in Examples 5 and 6).

  The amount of dispersed oxidant according to the method of the present invention depends on the amount of organic material in the water. Calcium hypochlorite or NaDCC interacts with organic materials when contacted, thereby rapidly reducing their effective concentration. That is, the active compound in the suspension formulation interacts immediately with the organic load in the water and does not accumulate without leaving any detectable residue in the environment.

  The present invention also provides sustained release suspension formulations of bleaching compounds. Specifically, the present invention provides a buoyant composition comprising a planktonic algae growth inhibitor, a planktonic aquatic insect ovicide, or a compound that reduces insect spawning on water.

  While not wishing to be bound by theory, the present invention provides a simple and cost-effective way to interfere with the ecological status of cyanobacteria or green algae (phytoplankton). This interference provides temporary benefits to competing microorganisms in the same environment, making them superior and competing with harmful phytoplankton successfully. That is, the method of the present invention is not intended to completely remove cyanobacteria or green algae from the water area as is common with antibiotics, but for temporary changes in their ecological status. It aims to provide a means. Such a method has never been used in wide river watersides.

  In another embodiment, particularly for the treatment of aquatic insects, eggs or larvae, the total concentration of oxidizing agent (eg, calcium hypochlorite or NaDCC) is about 50 ppm, or 100 ppm, or 200 ppm, or 250 ppm of active agent. Or 300 ppm, or 400 ppm, or 500 ppm, or 600 ppm, or 700 ppm, or 800 ppm, or 900 ppm, or 1000 ppm or more. In one embodiment, the total concentration of oxidizing agent is between about 50 ppm and about 1000 ppm of active agent. Preferably, the total concentration of oxidizer is between about 50 ppm and about 500 ppm of the active agent.

  With respect to aquatic insects, bleach has not been proposed as a commercially available egg killer. Probably because high levels of oxidant could not reach and maintain the egg position at the water surface (Di Domenico et al., 2006; Hatchett, 1946; Jacups et al., 2013).

  As used herein, the term “ovicide” relates to an agent that kills or damages insect eggs, thereby inhibiting the normal hatching of insects and the growth of larvae to adults.

  As shown in Example 5 below, the concentration of hypochlorous acid disappears rapidly from the body of water (reacts with any kind of organic material) in the natural environment. These hypochlorous acid concentrations had a very effective effect on phytoplankton, as shown in Example 5, but they were either mosquito eggs or mosquitoes that escaped the active compound by swimming away. It did not affect the larvae effectively. In contrast, a series of experiments on different types of aquatic insects shown in Example 7 show that relatively high concentrations of bleach (eg, NaDCC) are required to destroy insect eggs. Since these insect eggs are usually laid in large waters, treating the waters with non-buoyant formulations will dilute the bleach load throughout the waters, thus affecting the insect eggs. Without effective concentrations can be reached to cause early hatching of insect larvae. The buoyant formulation of the present invention thus provides an effective solution and allows for the administration of high concentrations (eg 50-500 ppm) of oxidant required for effective treatment at the water surface, thereby achieving the desired killing. Can produce egg effect.

  In addition, the process by which female mosquitoes lay eggs has been investigated for decades. Without wishing to be bound by theory, female mosquitoes can detect harmful environments before laying eggs on the surface of the water. Therefore, it is expected that the amount of eggs laid in an aquatic system will be considerably reduced by using a floating sustained-release preparation comprising a bleaching agent.

Example 1: Determination of sensitivity of cyanobacteria to hypochlorite

A 4 liter glass bottle (diameter = 65 mm, height = 1210 mm) was filled with CHAB collected recently from the Bible Zoo in Jerusalem (FIG. 1A). The massive algae population consisted mainly of Microcystis sp. This contaminated water was treated overnight with a suspension of calcium hypochlorite. The floating formulation was prepared by placing calcium hypochlorite particles on floating paper. The contaminated water gradually wets the floating paper, and the calcium hypochlorite particles gradually dissolved in the glass bottle while reacting with the organic substance and forming a concentration gradient in the water. After overnight treatment with a suspension formulation containing 0.5 mg of calcium hypochlorite per square centimeter (FIG. 1B), the average concentration of hypochlorite in the glass bottle is at an acceptable level in drinking water ( 0.03 mM), which is well below 0.075 mM). Algae on the water surface dissolved. The eukaryotic algae at the bottom of the glass bottle were not affected because the concentration of calcium hypochlorite was low at the bottom. Chlorine odor was not detectable at any stage of the experiment.
Example 2: Testing various calcium hypochlorite concentrations

Experiments were performed as shown above in Example 1 with various concentrations of calcium hypochlorite. As shown in FIG. 2, different concentrations of Ca (OCl) ₂ were added to 4 liter glass bottles: (A) untreated, (B) 0.05 mg / 1 cm ₂ Ca (OCl) ₂ , (C) 0 1 mg / 1 cm ₂ Ca (OCl) ₂ , (D) 0.5 mg / 1 cm ₂ Ca (OCl) ₂ . At the end of the experiment, 2 mL from the water surface of each tank was transferred to a 10 mL vial and allowed to settle for several minutes. FIG. 2 shows the effect of various concentrations. Each concentration tested reduced the amount of algal population.
Example 3: Preparation of a floating composition of anhydrous NaDCC using beeswax

Anhydrous NaDCC (Sig / m2a # 218890) was thoroughly mixed with beeswax preheated to 50 ° C. at 1: 1 wt%. This formed NaDCC fine particles partially encapsulated with beeswax that could float the active ingredient on the water surface.
Example 4: Preparation of an exemplary suspension formulation containing NaDCC

An exemplary product formulation included the following ingredients:
Active ingredient: Sodium dichloroisocyanurate NaDCC dihydrate (obtained from Acros Chemical)-39.4% by weight of total formulation
Gelling agent: Hydroxypropyl methylcellulose (Methocel 40-202PCG obtained from DOW Chemical)-42.4% by weight of total formulation
Binder: Glyceryl stearate (obtained from Making Cosmetics)-10.2% by weight of total formulation
Swelling agent: NaCl (obtained from Sig / m2a Aldrich)-8% by weight of total formulation
Alternatively, citric acid (obtained from Sig / m2a Aldrich) and sodium bicarbonate (obtained from Chem-IMPEX INT'L, Inc.)-each 4% by weight of total formulation
Preparation method

The product formulation was prepared as follows: NaCl, citric acid and sodium dichloroisocyanurate dihydrate (NaDCC) were crushed in separate containers to a particle size in the range of about 0.2-0.7 mm. . Alternatively, NaCl was replaced with glyceryl stearate and sodium bicarbonate. This produces particles that can be uniformly distributed throughout the product. Next, Methocel 40-202PCG, glyceryl stearate, sodium dichloroisocyanurate dihydrate, citric acid, and sodium bicarbonate were combined in a large container and stirred until all ingredients were well mixed. Once mixed well, the mixture was placed in a 12 mm diameter pellet press. The pellet press was adjusted to produce pellets having a thickness of about 7 mm and a mass of about 500 mg. The pellet was then incubated in a 115 ° C. orb for 3 minutes, removed from the oven and allowed to cool.
Dissolution test

  The ability of the pellet to release free available chlorine from water-soluble NaDCC was measured over time using a colorimetric method. Three pellets were randomly selected from the produced kilogram batches. The size and mass of each pellet was recorded, and the pellet was placed in an 800 mL high density polyethylene (HDPE) beaker filled with deionized water and covered with aluminum foil. The dimensions and mass of randomly selected pellets are reported in Table 1. As a control, NaDCC (0.1975 g) was added to another 800 mL plastic beaker. A 0.8 mL aliquot of each solution was pipetted into a 50 mL volumetric flask and the volume adjusted with deionized water. 10 mL aliquots of these diluted solutions were mixed with 100 μL of 0.1% orthotolidine in a vial to form a clear yellow solution. This solution was placed in a cuvette and analyzed at 436 nm using a Shimadzu UV160U UV-Vis spectrophotometer.

  The first sample was taken 15 minutes after adding the pellet and control sample to the test water. In addition, additional samples were taken at approximately 2, 9, 11, 13, 15, 17, 24, and 36 hours.

Upon exposure to water, NaDCC decomposes and releases free available chlorine that acts as an inhibitor of algal growth. Orthotolidine reacts with chlorine, causing discoloration and allows colorimetric analysis to chart NaDCC dissolution. The concentration of NaDCC released at each time point was calculated by constructing a calibration curve relating the response of free available chlorine to the initial concentration of NaDCC. The calculation of the initial concentration of NaDCC is shown in Equation 1. Standards were made in the range of 25-250 ppm using the first aliquot of the control taken at the 15 minute time point. Table 2 shows the instrument response of each standard solution.
Formula 1: Initial concentration of NaDCC = Initial mass of NaDCC / Deionized water volume 197.5 mg / 0.800 L = 246.9 ppm

The concentration of NaDCC released over time by the pellet was calculated using the relationship found between the concentration and the response from the calibration curve, also shown in Equation 2. The responses and controls for each randomly selected pellet (labeled “A”, “B” and “C”) are reported in Table 3.
Equation 3 was used to convert the response to the concentrations in Table 3.
Formula 2: Response (AU) = 0.0085 × Concentration (ppm)
Formula 3: Concentration (ppm) = Response (AU) /0.0085

  As shown above, the exemplified formulation floats and gradually releases NaDCC over time.

NaDCC release occurred relatively linearly up to 15 hours. After 15 hours, the release rate dropped dramatically. By 15 hours, about 85% NaDCC was released and by 24 hours about 90% was released.
Example 5: Use of a suspension formulation to reduce cyanobacterial cell density [I]

Aerated fish pond (S10 pond, Auburn University) with a chlorophyll concentration of about 150 μg / L and a microcystin level of 0.2 μg / L, in which a toxic cyanobacterium Oscillatoria sp. , Auburn, AL.) Was equipped with an enclosure [transparent tube made of polyethylene having a radius of 20 cm and a length of 2.0 m, surface area (0.125 square m)]. Three independent assays were set up and treated with capsules (pellets) containing about 200 mg of sodium dichloroisocyanurate (NaDCC) dihydrate granules as the active ingredient. Capsules were prepared as shown in Example 4. The enclosure was opened towards the bottom of the pond and was subjected to water movement by a powerful aerator operating every morning for a few hours once a day. Four different treatments were applied: 8 capsules (1.6 g NaDCC dihydrate total) (1) 1 dose on day 1 only, (2) 1 dose each morning for 5 days (3 ) One dose twice a day for 5 days, and (4) no treatment. Samples were taken from all enclosures 3 hours after the morning treatment. The concentration of chlorophyll a was measured on the water surface and at a water depth of 50 cm. This measurement is accepted as a direct indicator of phytoplankton cell density. Also measured were dissolved oxygen (DO) level, pH (at all depths), total suspended matter (TSS) at the water surface, conductivity, and dimming. The following unexpected findings were observed:
1. Three hours after the first treatment, a 50-70% decrease in chlorophyll a concentration was observed on the water surface, which reached a 99.96% decrease over 5 days of treatment (FIG. 3A). Unexpectedly, this repeated treatment also affected the water column and a 50% -99% reduction in chlorophyll a was observed at 50 cm depth compared to day 0 and untreated controls (FIG. 3B).
2. Decreasing the number of cyanobacteria also resulted in a decrease in photosynthetic yield: lower consumption of CO ₂ from the system decreased carbonic acid resulting in increased bicarbonate concentration and therefore decreased pH level. The pH dropped from 8.0 to 4.0 (Figure 3C).
3. Due to the loss of photosynthetic yield, the dissolved oxygen (DO) measurement was also expected to decrease: the O ₂ concentration in water drops very quickly, ie after one day, the O ₂ concentration decreases by about 50%, measuring for 5 days. (FIG. 3D).
4). Despite a significant decrease in phytoplankton, the dimming measured along the water column, as well as TSS or conductivity, did not change unexpectedly.

  While not wishing to be bound by theory, pH and DO measurements clearly indicate that cyanobacterial physiology changed early in the treatment, just before the cyanobacterial cells began to disappear from the pond water. Shown in This hypothesis is supported by the fact that measurements of dimming coefficient, conductivity, and total suspended matter (TSS) have not changed. In addition, the measurements of these three parameters remain constant throughout the entire assay and are consistent across all three experimental blocks, with other populations of microorganisms taking ecological status when cyanobacteria are depleted. Suggests something has changed. Alternatively, other populations of microorganisms may have preyed on nutrient-containing cyanobacterial cell contents.

  Another support for the claim is that the chlorine concentration was hardly detectable across the entire assay, either at the water column or at the surface, and did not exceed 0.1-0.3 ppm after 3 hours of treatment. In this enclosure with a capacity of about 270 liters, 1.6 g NaDCC dihydrate should theoretically represent 5.9 ppm or ˜3.4 ppm available chlorine, but once a day or 1 Nothing was detected in any of the treatments twice a day. In other words, the effect of treatment on cell density as well as additional parameters cannot be explained solely by the direct toxic effects of this compound.

In addition, as mentioned above, this enclosure is placed about 20m away from a powerful aerator, which mixes the pond water daily and sprays the water from above or through the open end of the enclosure. The pond water was probably mixed with the water in the enclosure by pushing water out of the bottom. Correlation of all parameters in all three independent test blocks (water level and chlorophyll a concentration at 50 cm depth, pH and DO (FIGS. 3A-D)) It clearly shows that treatment with sex preparations can cause complete disruption of harmful cyanobacterial populations and may pave the way for other competing opportunistic microorganisms.
Example 6: Use of a suspension formulation to reduce cyanobacterial cell density [II]

In another experiment, a shallow (water depth 30-100 cm) aerated aquaculture pond (G16 pond, Auburn University) with a large amount of Oscillatoria sp. At an initial cell density of about 10 ⁶ filaments / mL. , Auburn, AL., USA) was equipped with an enclosure (consisting of a transparent polyethylene tube having a length of 40 cm). The enclosure was placed in the water, opening towards both the water surface and the bottom of the pond. The following treatments were applied: (1) untreated control, (2) treatment with 3 capsules NaDCC suspension, (3) treatment with 6 capsules NaDCC suspension, and (4) 9 capsules. Treatment with NaDCC suspension formulation (see FIG. 4 showing an exemplary enclosure). Each capsule contained NaDCC dihydrate as the active compound in the suspension formulation as described in Example 4. The treatment was carried out at 19:00 on the first day, then at 8:00 am on the second day, and then the third treatment was carried out at 12:00 on the second day.

Six capsules (as described above, a total of 1.2 g NaDCC dihydrate) successfully removed all scum in the enclosure (FIGS. 5 and 6). This was also demonstrated in vials filled with the water level of the enclosure, indicating relative turbidity across the process (Figure 7). The number of cells in the water surface dropped dramatically during the treatment process (one digit). The pH on the water surface dropped from pH 9.5 to pH 8, suggesting a decrease in photosynthetic activity. Total chlorine measurement was performed using a trace device (Pocket Tracer code 1740, LaMotte, USA). At the end of processing, the total chlorine concentration of 0.3 ppm for the 3 capsule treatment and the total chlorine concentration of 0.43 ppm for the 6 capsule treatment , And 9 capsule treatments revealed a total chlorine concentration of 1.22 ppm (total chlorine concentrations were well below the theoretically predicted concentrations of 8, 16 and 24 ppm for a volume of 43 liters, respectively).
Example 7: Clarifying the effect of anhydrous sodium dichloroisocyanurate (NaDCC) on various dangerous insects floating on the water

  A 3% concentration of household bleach did not harm the eggs of Stephenus anopheles (Anopheles stevensi), but moderate chlorine concentrations hatched many types of insect larvae faster than untreated controls. Early hatching changed their development and prevented them from transforming into adults.

A series of experiments on various types of aquatic insects, shown below, show that relatively high concentrations of bleach are required to destroy insect eggs.
a. C. quinquefasciatus

Mosquito eggs were obtained from the disease management center of Fort Collins, Colorado. Eggs are counted and transferred to drop plates containing 8 mL of NaDCC aqueous solution at 0, 50, 500, 5000 and 50,000 ppm, and each treatment concentration and control (0 ppm) is repeated three times in the same drop plate. It moved to the incubator set to 30 degreeC, and the brightness change of 12 hours was performed for 25 hours. Immediately when the eggs were transferred to pond water, many larvae in the control group began to hatch and began to swim. Twenty-five hours after starting the bioassay, larvae were counted as alive, post-hatched or unhatched. If the larvae were completely removed from the egg envelope, they were counted only as hatched. Data was analyzed by probit analysis using the PROBIT Procedure on SAS (version 9.2, Cary North Carolina) to obtain LC ₉₅ and natural response rate. The nettle squid LC ₉₅ was 93.8 ppm. Eggshells dissolved and could not be discerned with the 50,000 ppm treatment, and the 5000 ppm treatment was mostly dissolved, suggesting that the larvae still remain in shape and do not hatch.
b. Stephens Anopheles (Anpheles stephensi)

Stefen anopheles eggs were obtained from the collection of the New York University School of Medicine's Institute Core Facility and Parasite Culture. Sixty eggs were counted and transferred to a drip plate containing 8 mL of NaDCC aqueous solution at 0, 0.58, 5.8, 58, 580 and 5800 ppm. Each treatment and control was repeated three times in the same drop plate and transferred to an incubator set at 30 ° C. for a 12 hour light / dark change for 72 hours. Data were analyzed by probit analysis using the PROBIT Procedure on SAS (version 9.2, Cary North Carolina). 72 hours after the start of the bioassay, larvae were counted as alive, post-hatched or unhatched. When an individual was completely removed from the egg envelope, it was counted only as hatched. The LC ₉₅ for Stefense anopheles was 270 ppm.
c. Aedes aegypti

Aedes aegypti eggs were obtained from the disease management center of Fort Collins, Colorado. Eggs were counted and transferred to drip plate treatment or control wells, which were then placed in an incubator. 72 hours after the start of the bioassay, larvae were counted as alive, post-hatched or unhatched. If the larvae were completely removed from the egg envelope, they were counted only as hatched. Data was analyzed by probit analysis using the PROBIT Procedure on SAS (version 9.2, Cary North Carolina) to obtain LC ₉₅ and natural response rate. The LC ₉₅ of Aedes aegypti was 470 ppm. Eggshells dissolved and could not be discerned with the 50,000 ppm treatment, and the 5000 ppm treatment was mostly dissolved, suggesting that the larvae still remain in shape and do not hatch.
d. Chironomid (Chironomidae)

Non-Nukaka eggs (Chironomidae: Chironomidae) were purchased from Town Park, Auburn, AL. From the pond. Eggs were counted and transferred to drip plates containing 8 mL NaDCC aqueous solution at 0, 50, 500, 5000 and 50,000 ppm. Each treatment and control was repeated three times in the same drop plate and transferred to an incubator set at 30 ° C. for a 12 hour light / dark change for 1 week. Data were analyzed by probit analysis using the PROBIT Procedure on SAS (version 9.2, Cary North Carolina). If the larvae were completely removed from the egg envelope, they were counted only as hatched. The LC _{95 for the} subfamily Chironomidae was 205.7 ppm and the estimated natural mortality rate was 2.8%.

Claims (46)

A method for suppressing water surface inhabiting photosynthetic microbial blooms in an aquatic system,
a. Producing a buoyant composition comprising at least one photosynthetic microorganism inhibitor and a buoyant;
b. Using the buoyant composition on the surface of the aquatic system under conditions that induce a reduction of at least 50% of the photosynthetic microorganism within a period of time in the aquatic system, wherein the at least one photosynthetic microorganism An inhibitor is at a concentration less than that allowed in drinking water in the aquatic system after the period, and the at least one photosynthetic microbial inhibitor is adapted to substantially degrade from the aquatic system; Using, characterized in that, after said period, it cannot be detected in its active state;
Including a method.   The method of claim 1, wherein the at least one photosynthetic microorganism inhibitor comprises an oxidizing water disinfectant.   The method of claim 2, wherein the water disinfectant is selected from the group consisting of a chlorine release agent, a bromine release agent, a peroxide-based compound, a copper salt, an aluminum salt, and any combination thereof.   4. The method of claim 3, wherein the chlorine releasing agent is selected from calcium hypochlorite and sodium dichloroisocyanurate (NaDCC).   The method according to any one of claims 1 to 4, wherein the floater is selected from the group consisting of cellulose derivatives, plant biomass, saturated hydrocarbons, resinous materials, foams, waxes and natural or synthetic latex.   The method according to claim 5, wherein the floating agent is wood flour.   6. A method according to claim 5, wherein the flotation agent is paraffin.   The method according to claim 5, wherein the floating agent is rosin.   The method according to claim 5, wherein the floating agent is an extruded polystyrene foam or an expanded polystyrene foam.   The method of claim 5, wherein the floater is a silicone foam.   The concentration of the photosynthetic microbial inhibitor is about 10%, or about 20%, or about 30%, or about 40%, or about 50%, or more of the composition. The method of any one of 10-10.   6. A method according to any one of the preceding claims, wherein the composition is in the form of particles, granules, flakes, powders, pellets, pills, solutions or combinations thereof.   The method according to any one of claims 1 to 12, wherein the at least one photosynthetic microorganism is selected from the group consisting of cyanobacteria, algae, plactones and combinations thereof.   14. A method according to any one of the preceding claims, wherein the step of using follows detection of the bloom in the aquatic system.   The method of claim 14, wherein the step of using is performed during a seasonal bloom.   The method according to claim 1, wherein the period is 3 hours.   17. A method according to any one of the preceding claims, wherein the period is at least 3 days and the at least 50% reduction is at least 99% reduction. The photosynthetic microorganism is a cyanobacterium, wherein said composition is used in a concentration between the concentration or about 0.5ppm to about 50 ppm, between about 0.005 g / ^{m 2} and about 50 g / ^{m 2} of said inhibitor The method according to claim 1.   The method of claim 18, wherein the step of using is repeated after an interval of several hours.   As a result of the use step, the amount of the inhibitor is small when measured in water after 0.5 hour, 1 hour, 2 hours, 3 hours, 24 hours or more after each use. The method of claim 19.   19. A method according to claim 18 wherein the trace amount of active compound is 3 ppm or less as measured 24 hours after each use or later.   The treatment step is performed three times a day, twice a day or once a day, or once a week, or once every two weeks, or once every three weeks, or once a month, or The method of claim 18, wherein the method is performed at longer intervals.   The method according to claim 21, wherein the step of using is performed once a day or twice a day for a period of 1 day, 2 days, 3 days, 4 days, 5 days or more.   24. The method of claim 23, further comprising using a second inhibitor on the water surface.   The method of claim 1, wherein the step of using is performed by a manual or mechanical sprayer or by diffusing a liquid or foam from a boat or airplane. A diffusible airborne composition used to control blooms of waterborne photosynthetic microorganisms in an aquatic system,
A composition comprising a photosynthetic microorganism inhibitor and a flotation agent, wherein the composition is adapted to gradually release the inhibitor to the water surface to oxidize the bloom, and the at least one photosynthetic microorganism inhibitor A composition wherein the agent has a concentration less than that allowed for drinking water in the aquatic system after the period.   27. The composition of claim 26, wherein the photosynthetic microorganism inhibitor is an oxidizing water disinfectant.   28. The composition of claim 27, wherein the at least one water disinfectant is selected from the group consisting of chlorine release agents, bromine release agents, peroxide-based compounds, copper salts, aluminum salts, and any combination thereof. object.   29. The composition of claim 28, wherein the water disinfectant is calcium hypochlorite or NaDCC.   30. The composition according to any one of claims 27 to 29, wherein the floating agent is selected from the group consisting of cellulose derivatives, plant biomass, saturated hydrocarbons, resinous substances, foams, waxes and natural latex or synthetic latex. .   32. The composition of claim 30, wherein the floating agent is wood flour.   32. The composition of claim 30, wherein the floater is paraffin.   32. The composition of claim 30, wherein the floater is rosin.   32. The composition of claim 30, wherein the floater is an extruded polystyrene foam or expanded polystyrene foam.   32. The composition of claim 30, wherein the floater is a silicone foam.   32. The composition of claim 30, wherein the floater is a wax.   37. A composition according to any one of claims 26 to 36, wherein the composition is in the form of particles, granules, flakes, powders, pellets, pills, or solutions.   38. The composition of any one of claims 26 to 37, wherein the photosynthetic pest growth is selected from the group consisting of cyanobacterial growth, algae growth, microbial growth, and plankton growth.   39. The composition of any one of claims 26 to 38, wherein the composition is suitable for administration following detection of harmful blooms in the aquatic system. Between said pest is a cyanobacteria, and the concentration of between about 0.005 g / ^{m 2} and about 50 g / ^{m 2} of at least one water disinfectant active agent or from about 0.5ppm to about 50 ppm, 30. The composition of claim 28, administered at a concentration of.   The amount of the at least one water disinfectant is about 10%, or about 20%, or about 30%, or about 40%, or about 50%, or more of the total composition, Item 38. The composition according to any one of Items 28 to 37.   The active compound as a result of administration of the composition to the aquatic system as measured in water 0.5 hours, 1 hour, 2 hours, 3 hours, 24 hours or more after each treatment 42. The composition of claim 41, wherein is in trace amounts.   43. The composition of claim 42, wherein the trace amount of active compound does not exceed 3 ppm as measured 24 hours after each treatment or later.   27. The composition of claim 26, wherein the composition is adapted for one, two or more administrations to the aquatic system.   An administration wherein the composition is administered three times a day, twice a day or once a day, or once a week, or once every two weeks, or once every three weeks, or once a month, or 44. The composition of claim 43, suitable for administration administered at longer intervals.   44. The composition of claim 43, wherein the composition is adapted for administration administered once daily or twice daily for a period of 1 day, 2 days, 3 days, 4 days, 5 days or more. object.

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